Cyclopenta[b]Fluorenyl Transition Metal Compound, Catalyst Composition Containing the Same, and Method of Preparing Ethylene Homopolymer or Copolymer of Ethylene and Alpha-Olefin Using the Same

ABSTRACT

The present invention relates to a new transition metal compound based on cyclopenta[b]fluorenyl group, a transition metal catalyst composition containing the same and having high catalytic activity for preparing an ethylene homopolymer or a copolymer of ethylene and one α-olefin, a method of preparing an ethylene homopolymer or a copolymer of ethylene and α-olefin using the same, and the prepared ethylene homopolymer or the copolymer of ethylene and α-olefin.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. application Ser.No. 15/832,011, filed Dec. 5, 2017, which is a divisional application ofU.S. application Ser. No. 14/789,512, filed Jul. 1, 2015, now U.S. Pat.No. 9,926,394, issued Mar. 27, 2018, which is a divisional applicationof U.S. application Ser. No. 13/881,098, filed Apr. 23, 2013, now U.S.Pat. No. 9,120,884, issued Sep. 1, 2015, which is a United Statesnational phase application under 35 U.S.C. § 371 of InternationalApplication No. PCT/KR2012/004511 filed Jun. 8, 2012, and claimspriority under 35 U.S.C. § 119(a)-(d) to Korean Patent Application Nos.10-2012-0059441 filed on Jun. 1, 2012, and 10-2011-0055719, filed onJun. 9, 2011 in the Korean Intellectual Property Office, the disclosuresof which are incorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a new transition metal compound basedon cyclopenta[b]fluorenyl group, a transition metal catalyst compositioncontaining the same and having high catalytic activity for preparing anethylene homopolymer or a copolymer of ethylene and one α-olefin, amethod of preparing an ethylene homopolymer or a copolymer of ethyleneand α-olefin using the same, and the prepared ethylene homopolymer orthe copolymer of ethylene and α-olefin. More particularly, the presentinvention relates to a transition metal compound that is advantageous inobtaining high-efficiency and high-molecular weight ethylene-basedpolymers by having a structure where a Group 4 transition metal in thePeriodic Table of Elements as a core metal is linked with acyclopenta[b]fluorenyl group that has a rigid plane structure eventhough it is not in a hetero ring; has abundant electrons widelynon-localized; and allows a substituent contributing to improvement insolubility and performance to be easily inducible at position 9 thereof,via an amido group substituted with a silyl group, a transition metalcatalyst composition containing the transition metal compound as aprimary catalyst and an aluminum compound, a boron compound, or amixture thereof as cocatalyst, for preparing an ethylene homopolymer ora copolymer of ethylene and at least one α-olefin, a method of preparingan ethylene homopolymer or a copolymer of ethylene and α-olefin usingthe same, and the prepared ethylene homopolymer or the copolymer ofethylene and α-olefin.

Description of Related Art

In the prior art, so-called Ziegler-Natta catalyst consisting of atitanium or vanadium compound as a primary catalyst component and analkylaluminum compound as cocatalyst component have been generally usedfor preparing ethylene homopolymers or copolymers of ethylene andα-olefin. Although a Ziegler-Natta catalytic system exhibits highactivity on ethylene polymerization, the catalytic system hasdisadvantages in that molecular weight distribution of the producedpolymer is broad due to non-uniform catalyst activation point, andespecially, composition distribution thereof is not uniform in thecopolymers of ethylene and α-olefin.

Recently, so-called metallocene catalytic systems consisting of ametallocene compound of Group 4 transition metal in the Periodic Tableof Elements, such as titanium, zirconium and hafnium, andmethylaluminoxane as a cocatalyst have been developed. The metallocenecatalytic system is a homogeneous catalyst having a mono-modal catalystactivation point, and thus, can provide prepare polyethylene havingnarrower molecular weight distribution and more homogenous compositiondistribution as compared with the existing Ziegler-Natta catalystsystem. For example, European Patent Laid-Open Publication Nos. 320,762and 372,632; Japanese Patent Laid-Open Publication Nos. Sho 63-092621,Hei 02-84405 and Hei 03-2347 reported that ethylene may be polymerizedwith high activity by activating metallocene compounds such as Cp₂TiCl₂,Cp₂ZrCl₂, Cp₂ZrMeCl, Cp₂ZrMe₂, ethylene(IndH₄)₂ZrCl₂ by usingmethylaluminoxane as a cocatalyst, to prepare polyethylene having amolecular weight distribution (Mw/Mn) in the range from 1.5 to 2.0.However, it is difficult to obtain high-molecular weight polymers byusing the above catalytic system, and further, when solutionpolymerization executed at a high temperature of 100° C. or higher isemployed, polymerizing activity abruptly decreases and β-dehydrogenationis predominant. Therefore, the system has been known to be not suitablefor preparing high-molecular weight polymers having a weight averagemolecular weight (Mw) of 100,000 or more.

Meanwhile, there was reported so-called geo-restrictive non-metallocenebased catalysts (also referred to as single activation point catalysts)where the transition metals are linked in a ring type, as catalysts forpreparing high-molecular weight polymers with high catalytic activity inethylene homopolymerization or copolymerization of ethylene and α-olefinin the solution polymerization conditions. European Patent Nos. 0416815and 0420436 suggest an example where amide group is linked to onecyclopentadiene ligand in a ring type, and European Patent No. 0842939shows an example of the catalyst where phenol-based ligand as anelectron donor compound is linked to cyclopentadiene ligand in a ringtype. This geo-restrictive catalyst may remarkably improve reactivitywith higher α-olefins due to lowered sterical hindrance effect of thecatalyst itself, but has many difficulties in the commercial usethereof. Therefore, it has been important to secure more competitivecataltytic systems in requiring commercialized catalysts based oneconomical feasibility, that is, excellent high-temperature activity,excellent reacitivity with higher α-olefins, and capability to preparehigh-molecular weight polymers.

SUMMARY OF THE INVENTION

In order to overcome the problems of the prior art, the presentinventors conducted extensive studies, and found that a transition metalcompound having a structure where a Group 4 transition metal in thePeriodic Table of Elements as a core metal is linked with acyclopenta[b]fluorenyl group that has a rigid plane structure eventhough it is not in a hetero ring; has abundant electrons widelynon-localized; and allows a substituent contributing to improvement insolubility and performance to be easily inducible at position 9 thereof,via an amido group substituted with a silyl group was advantageous inobtaining high-efficiency and high-molecular weight polymers inpolymerization of ethylene and olefins, and thus, completed the presentinvention.

An object of the present invention is to provide a transition metalcompound useful as a catalyst for preparing ethylene homopolymers orcopolymers of ethylene and α-olefin, and provide a catalyst compositioncontaining the same.

Another object of the present invention is to provide a method ofeconomically preparing ethylene homopolymers or copolymers of ethyleneand α-olefin using the catalyst composition containing the transitionmetal compound in a view of commertialization.

Still another object of the present invention is to provideethylene-based polymers selected from the ethylene homopolymers and thecopolymers of ethylene and α-olefin prepared by the above method.

DESCRIPTION OF THE INVENTION

An aspect of the present invention for achieving the above objectsprovides a new transition metal compound based on acyclopenta[b]fluorenyl group represented by Chemical Formula 1 below.More specifically, the present invention relates to a transition metalcompound that is advantageous in obtaining high-efficiency andhigh-molecular weight ethylene-based polymers by having a structurewhere a Group 4 transition metal in the Periodic Table of Elements as acore metal is linked with a cyclopenta[b]fluorenyl group that has arigid plane structure even though it is not in a hetero ring; hasabundant electrons widely non-localized; and allows a substituentcontributing to improvement in solubility and performance to be easilyinducible at position 9 thereof, via an amido group substituted with asilyl group.

In Chemical Formula 1, M is a Group 4 transition metal in the PeriodicTable of Elements;

n is an integer of 1 or 2, each R₁ may be the same or different when nis 2;

R₁ is hydrogen, (C1-C50)alkyl, halo(C1-C50)alkyl, (C3-C50)cycloalkyl,(C6-C30)aryl, (C6-C30)aryl(C1-C50)alkyl,((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl, —NR^(a)R^(b),—SiR^(c)R^(d)R^(e), or 5- through 7-membered N-heterocycloalkylcontaining at least one nitrogen atom;

R₂ and R₃ each are independently hydrogen, (C1-C50)alkyl,(C1-C50)alkoxy, halo(C1-C50)alkyl, (C3-C50)cycloalkyl, (C6-C30)aryl,(C6-C30)aryloxy, (C1-C50)alkyl(C6-C30)aryloxy,(C6-C30)aryl(C1-C50)alkyl, ((C1-C50)alkyl(C6-C30)arylC1-C50)alkyl,—NR^(a)R^(b) or —SiR^(c)R^(d)R^(e);

R₄, R₅, R₁₀, R₁₁ and R₁₂ each are independently (C1-C50)alkyl,halo(C1-C50)alkyl, (C3-C50)cycloalkyl, (C6-C30)aryl,(C6-C30)aryl(C1-C50)alkyl, ((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl,—NR^(a)R^(b), or —SiR^(c)R^(d)R^(e), and R₁₁ and R₁₂ may be linked via(C4-C7)alkylene to form a ring;

R₆, R₇, R₈ and R₉ each are independently hydrogen, (C1-C50)alkyl,halo(C1-C50)alkyl, (C3-C50)cycloalkyl, (C1-C50)alkoxy, (C6-C30)aryl,(C6-C30)aryl(C1-C50)alkyl, ((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl,(C6-C30)aryloxy, (C1-C50)alkyl(C6-C30)aryloxy, N-carbazolyl,—NR^(a)R^(b), or —SiR^(c)R^(d)R^(e), or may be linked to an adjacentsubstituent via (C1-C5)alkylene to form a ring, and at least one —CH₂—of the alkylene may be substituted by a hetero atom selected from —O—,—S—, and —NR′—, and the alkylene may be further substituted with(C1-C50)alkyl;

aryl of R₁ to R₁₂ may be further substituted with at least onesubstituent selected from the group consisting of (C1-C50)alkyl,halo(C1-C50)alkyl, (C1-C50)alkoxy, (C6-C30)aryloxy, (C6-C30)aryl,(C1-C50)alkyl(C6-C30)aryl, and (C6-C30)aryl(C1-C50)alkyl;

R′ and R^(a) to R^(e) each are independently (C1-C50)alkyl or(C6-C30)aryl; and

X₁ and X₂ each are independently halogen, (C1-C50)alkyl,(C2-C50)alkenyl, (C3-C50)cycloalkyl, (C6-C30)aryl,(C6-C30)aryl(C1-C50)alkyl, ((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl,(C1-C50)alkoxy, (C6-C30)aryloxy, (C1-C50)alkyl(C6-C30)aryloxy,(C1-C50)alkoxy(C6-C30)aryloxy, (C1-C50)alkylidene, or an anion ordianion ligand consisting of 60 or less atoms containing N, P, O, S, Si,and halogen, except hydrogen, provided that one of X₁ and X₂ is adianion ligand, the other is ignored.

An example of the new transition metal compound based on thecyclopenta[b]fluorenyl group represented by Chemical Formula 1 above mayinclude a transition metal compound represented by Chemical Formula 2 or3 below:

In Chemical Formulas 2 and 3, M, R₂ to R₁₂, X₁ and X₂ has the samedefinition in Chemical Formula 1; R₂₁ and R₂₂ each are independentlyhydrogen, (C1-C50)alkyl, halo(C1-C50)alkyl, (C3-C50)cycloalkyl,(C6-C30)aryl, (C6-C30)aryl(C1-C50)alkyl,((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl, —NR^(a)R^(b),—SiR^(c)R^(d)R^(e), or 5- through 7-membered N-heterocycloalkylcontaining at least one nitrogen atom; aryl of R₁ may be furthersubstituted with at least one substituent selected from the groupconsisting of halogen, (C1-C50)alkyl, halo(C1-C50)alkyl, (C1-C50)alkoxy,(C6-C30)aryloxy, (C6-C30)aryl, (C1-C50)alkyl(C6-C30)aryl, and(C6-C30)aryl(C1-C50)alkyl; and R^(a) to R^(e) each are independently(C1-C50)alkyl or (C6-C30)aryl.

Another aspect of the present invention for achieving the objects of thepresent invention provides a transition metal catalyst compositioncontaining the transition metal compound, and a cocatalyst selected froman aluminum compound, a boron compound, or a mixture thereof.

Still another aspect of the present invention for achieving the objectsof the present invention provides a method of preparing anethylene-based polymer selected from an ethylene homopolymer and acopolymer of ethylene and α-olefin by using the transition metalcompound or the transition metal catalyst composition, and the preparedethylene homopolymer or copolymer of ethylene and α-olefin.

Hereinafter, the present invention will be described in more detail.

The Group 4 transition metal in the Periodic Table of Elements, M, ispreferably titanium (Ti), zirconium (Zr), or hafnium (Hf).

The term “alkyl” described herein includes a straight chain type or abranched chain type.

The term “aryl” described herein is an organic radical derived fromaromatic hydrocarbon by the removal of one hydrogen atom, and mayinclude a single ring or a fused ring containing, properly 4 to 7 ringatoms, and preferably 5 or 6 ring atoms. Specific examples thereofinclude phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl,triphenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl,or the like, but are not limited thereto.

For example, (C1-C50)alkyl may be methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl,n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl,n-pentadecyl, n-octadecyl, n-icosyl, or n-docosyl; (C3-C50)cycloalkylmay be, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, cyclodecyl, or cyclododecyl; (C6-C30)aryl or(C1-C50)alkyl(C6-C30)aryl may be, for example, phenyl, 2-tolyl, 3-tolyl,4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl,3,5-xylyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl,2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl,2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl,2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl,n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl,tert-butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl,n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl,biphenyl, fluorenyl, triphenyl, naphthyl, or anthracenyl;(C6-C30)aryl(C1-C50)alkyl or ((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkylmay be, for example, benzyl, (2-methylphenyl)methyl,(3-methylphenyl)methyl, (4-methylphenyl)methyl,(2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl,(2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl,(3,4-dimethylphenyl)methyl, (4,6-dimethylphenyl)methyl,(2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl,(2,3,6-trimethyl-phenyl)methyl, (3,4,5-trimethylphenyl)methyl,(2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl,(2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl,(pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl,(isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl, or anthracenylmethyl; and(C1-C50)alkoxy may be, for example, methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy,neopentyloxy, n-hexyloxy, n-octyloxy, n-dodecyloxy, n-pentadecyloxy, orn-eicosyloxy.

Preferably, each R₁ is independently hydrogen, methyl, ethyl, n-propyl,isopropyl, n-butyl, phenyl, naphthyl, biphenyl, 2-isopropylphenyl,3,5-xylyl, 2,4,6-trimethylphenyl, benzyl, dimethylamino, or pyrrolidino;

preferably, R₂ and R₃ are independently hydrogen, methyl, ethyl,n-propyl, isopropyl, n-butyl, phenyl, naphthyl, biphenyl,2-isopropylphenyl, 3,5-xylyl, 2,4,6-trimethylphenyl, benzyl, methoxy,ethoxy, isopropoxy, phenoxy, 4-tert-butylphenoxy, or naphthoxy;

preferably, R₄ and R₅ each are independently methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, 2-methylbutyl, sec-butyl, tert-butyl,n-pentyl, neopentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl,n-tetradecyl, n-hexadecyl, n-pentadecyl, n-octadecyl, n-icosyl,n-docosyl, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl,2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl,2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl,3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, biphenyl, fluorenyl, triphenyl, naphthyl,anthracenyl, benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl,(4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl,(2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl,(2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl,(4,6-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl,(2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl,(3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl,(2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl,(2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl,(ethylphenyl)methyl, (n-prop ylphenyl)methyl, (isopropylphenyl)methyl,(n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl, anthracenylmethyl,4-methoxyphenyl, 3,4-dimethoxyphenyl, or4-(hexyloxy)-3,5-dimethylphenyl;

preferably, R₆ to R₉ each are independently hydrogen, methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, 2-methylbutyl, sec-butyl,tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, n-octyl, n-decyl,n-dodecyl, n-pentadecyl, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl,2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl,2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl,2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, biphenyl, fluorenyl,2,7-di-tert-butyl-9-p-tolyl-9H-fluoren-9-yl, triphenyl, naphthyl,anthracenyl, benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl,(4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl,(2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl,(2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl,(4,6-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl,(2,3,5-trimethylphenyl)methyl, (2,3,6-trimethyl-phenyl)methyl,(3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl,(2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl,(2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl,(ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl,(n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl, anthracenylmethyl,4-methoxyphenyl, 3,4-dimethoxyphenyl, methoxy, ethoxy, isopropoxy,n-butoxy, n-hexyloxy, 2-methylbutyl, phenoxy, 4-tert-butylphenoxy,naphthoxy, trimethylsilyl, triphenylsilyl, dimethylamino, diphenylamino,or 9H-carbazol-9-yl, or may be linked to an adjacent substitutent via

to form a ring, L₁ and L₂ each are independently —O—, —S—, or —NR′—[each R′ is independently (C1-C50)alkyl or (C6-C30)aryl], R₃₁ to R₃₄each, independently, have the same definition as R₄ and R₅, and morepreferably, hydrogen, methyl or n-tetradecyl;

preferably, R₁₁ and R₁₂ each are independently methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, 2-methylbutyl, sec-butyl, tert-butyl,n-pentyl, neopentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl,n-pentadecyl, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl,2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl,2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl,3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, biphenyl, fluorenyl, triphenyl, naphthyl,anthracenyl, benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl,(4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl,(2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl,(2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl,(4,6-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl,(2,3,5-trimethylphenyl)methyl, (2,3,6-trimethyl-phenyl)methyl,(3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl,(2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl,(2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl,(ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl,(n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-tetradecylphenyl)methyl, naphthylmethyl,anthracenylmethyl, 4-methoxyphenyl, or 3,4-dimethoxyphenyl, or R₁₁ andR₁₂ may be linked to each other via butylene or pentylene to form aring;

R₁₀ is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,2-methylbutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl,n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl, cyclohexyl, phenyl,2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl,3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl,2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl,2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl,2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl,n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl,tert-butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl,n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl,biphenyl, fluorenyl, triphenyl, naphthyl, anthracenyl, benzyl,(2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl,(2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl,(2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl,(3,4-dimethylphenyl)methyl, (4,6-dimethylphenyl)methyl,(2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl,(2,3,6-trimethyl-phenyl)methyl, (3,4,5-trimethylphenyl)methyl,(2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl,(2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl,(pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl,(isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl, anthracenylmethyl,2-methoxyphenyl, or 3,4-dimethoxyphenyl.

In the definitions of substituents X₁ and X₂, examples of halogen atommay include fluorine, chlorine, bromine, and iodine atom; examples of(C1-C50)alkyl may include methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, n-octyl,n-decyl, n-dodecyl, n-pentadecyl, and n-eicosyl; examples of(C3-C50)cycloalkyl may include cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, and adamantyl; examples of (C6-C30)aryl mayinclude phenyl and naphthyl; examples of (C6-C30)aryl(C1-C50)alkyl or((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl may include benzyl,(2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl,(2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl,(2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl,(3,4-dimethylphenyl)methyl, (4,6-dimethylphenyl)methyl,(2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl,(2,3,6-trimethyl-phenyl)methyl, (3,4,5-trimethylphenyl)methyl,(2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl,(2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl,(pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl,(isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-dodecylphenyl)methyl,(n-tetradecylphenyl)methyl, naphthylmethyl, and anthracenylmethyl;examples of (C1-C50)alkoxy may include methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy,neopentyloxy, n-hexyloxy, n-octyloxy, n-dodecyloxy, n-pentadecyloxy, andn-eicosyloxy; examples of (C6-C30)aryloxy may include phenoxy,4-tert-butylphenoxy, or 4-methoxyphenoxy, the anion or dianion ligandconsisting of 60 or less atoms containing N, P, O, S, Si, and halogen,except for hydrogen may be —OSiR^(f)R^(g)R^(h), —SR^(i) [R^(f) to R^(i)each are independently (C1-C50)alkyl, (C6-C30)aryl, (C3-C50)cycloalkyl],—NR^(j)R^(k), or —PR^(l)R^(m) [R^(j) to R^(m) each are independently(C1-C50)alkyl, (C6-C30)aryl, (C6-C30)aryl(C1-C50)alkyl,(C3-C50)cycloalkyl, tri(C1-C50)alkylsilyl, or tri(C6-C30)arylsilyl].Examples of —OSiR^(f)R^(g)R^(h) may include trimethylsiloxy,triethylsiloxy, tri-n-propylsiloxy, triisopropylsiloxy,tri-n-butylsiloxy, tri-sec-butylsiloxy, tri-tert-butylsiloxy,tri-isobutylsiloxy, tert-butyldimethylsiloxy, tri-n-pentylsiloxy,tri-n-hexylsiloxy, or tricyclohexylsiloxy; examples of —NR^(j)R^(k) mayinclude dimethylamino, diethylamino, di-n-propylamino, diisopropylamino,di-n-butylamino, di-sec-butylamino, di-tert-butylamino, diisobutylamino,tert-butylisopropylamino, di-n-hexylamino, di-n-octylamino,di-n-decylamino, diphenylamino, dibenzylamino, methylethylamino,methylphenylamino, benzylhexylamino, bis(trimethylsilyl)amino, orbis(tert-butyldimethylsilyl)amino; examples of —PR^(l)R^(m) may includedimethylphosphine, diethylphosphine, di-n-propylphosphine,diisopropylphosphine, di-n-butylphosphine, di-sec-butylphosphine,di-tert-butylphosphine, diisobutylphosphine,tert-butylisopropylphosphine, di-n-hexylphosphine, di-n-octylphosphine,di-n-decylphosphine, diphenylphosphine, dibenzylphosphine,methylethylphosphine, methylphenylphosphine, benzylhexylphosphine,bis(trimethylsilyl)phosphine, andbis-(tert-butyldimethylsilyl)phosphine; examples of —SR^(i) may includemethylthio, ethylthio, propylthio, isopropylthio, butylthio, orisopentylthio.

X₁ and X₂ each are independently fluorine, chlorine, bromine, methyl,ethyl, isopropyl, amyl, benzyl, methoxy, ethoxy, isopropoxy,tert-butoxy, phenoxy, 4-tert-butylphenoxy, trimethylsiloxy,tert-butyldimethylsiloxy, dimethylamino, diphenylamino,dimethylphosphino, diethylphosphino, diphenylphosphino, ethylthio, orisopropylthio.

The transition metal compound of the present invention may be selectedfrom compounds of the structures below, but is not limited thereto:

M is Ti, Zr, or Hf; and X₁ and X₂ each have the same definition asdefined in Chemical Formula 1 above.

Meanwhile, in order to be an active catalyst component to be used forpreparing ethylene based polymers selected from ethylene homopolymersand copolymers of ethylene and α-olefin, the transition metal compoundaccording to the present invention may be preferably employed togetherwith, as cocatalyst, an aluminoxane compound, a boron compound, or amixture thereof, which can extract an X₁ or X₂ ligand from thetransition metal complex to cationize the core metal and act as acounterion having weak bond strength, that is, an anion, and thecatalyst composition containing the transition metal compound and thecocatalyst is also within the scope of the present invention.

The boron compound usable as the cocatalyst in the present invention hasbeen known in U.S. Pat. No. 5,198,401, and may be selected from boroncompounds represented by Chemical Formulas 4 to 6 below.

B(R⁴¹)₃  [Chemical Formula 4]

[R⁴²]⁺[B(R⁴¹)₄]⁻  [Chemical Formula 5]

[(R⁴³)_(p)ZH]⁺[B(R⁴¹)₄]⁻  [Chemical Formula 6]

[In Chemical Formulas 4 to 6, B is a boron atom;

R⁴¹ is phenyl, and the phenyl may be further substituted with 3 to 5substituents selected from a fluorine atom, (C1-C50)alkyl substituted orunsubstituted with a fluorine atom, or (C1-C50)alkoxy substituted orunsubstituted with a fluorine atom;

R⁴² is (C5-C7)aromatic radical or (C1-C50)alkyl(C6-C20)aryl radical,(C6-C30)aryl(C1-C50)alkyl radical, for example, triphenylmethyl radical;

Z is a nitrogen or phosphorus atom;

R⁴³ is (C1-C50)alkyl radical, or anilinium radical substituted with anitrogen atom and two (C1-C10)alkyl groups; and p is an integer of 2 or3.]

Preferable examples of the boron based cocatalyst may includetris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane,tris(2,3,4,5-tetrafluorophenyl)borane,tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane,phenylbis(pentafluorophenyl)borane, tetrakis(pentafluorophenyl)borate,tetrakis(2,3,5,6-tetrafluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,tetrakis(2,2,4-trifluorophenyl)borate,phenylbis(pentafluorophenyl)borate, andtetrakis(3,5-bistrifluoromethylphenyl)borate. In addition, certaincompounded examples thereof may include ferroceniumtetrakis(pentafluorophenyl)borate, 1,1′-dimethylferroceniumtetrakis(pentafluorophenyl)borate, tetrakis(pentafluorophenyl)borate,triphenylmethyl tetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis(3,5-bistrifluoromethylphenyl)borate, triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bistrifluoromethylphenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bistrifluoromethylphenyl)borate, diisopropylammoniumtetrakis(pentafluorophenyl)borate, dicyclohexylammoniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, and tri(dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate. Among them, preferable areN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis(pentafluorophenyl)borate, and tris(pentafluorophenyl)borane.

In the present invention, the aluminum compounds usable as thecocatalyst may selected from aluminoxane compounds of Chemical Formula 7or 8, organic aluminum compounds of Chemical Formula 9, or organicaluminum hydrocarbyloxide compounds of Chemical Formula 10 or 11.

(—Al(R⁵¹)—O—)_(m)  [Chemical Formula 7]

(R⁵¹)₂Al—(—O(R⁵¹)—)_(q)—(R⁵¹)₂  [Chemical Formula 8]

(R⁵²)_(r)Al(E)_(3-r)  [Chemical Formula 9]

(R⁵³)₂AlOR⁵⁴  [Chemical Formula 10]

R⁵³Al(OR⁵⁴)₂  [Chemical Formula 11]

[In Chemical Formulas 7 to 11, R⁵¹ is (C1-C50)alkyl, preferably methylor isobutyl; m and q each are independently an integer of 5 to 20; R⁵²and R⁵³ each are independently (C1-C50)alkyl; E is a hydrogen or halogenatom; r is an integer of 1 to 3; and R⁵⁴ is (C1-C50)alkyl or(C6-C30)aryl.]

Specific examples of the aluminum compound may include aluminoxanecompounds, such as methylaluminoxane, modified methylaluminoxane,tetraisobutylaluminoxane; organic aluminum compounds, such astrialkylaluminum including trimethylaluminum, triethylaluminum,tripropylaluminum, triisobutylaluminum, and trihexylaluminum;dialkylaluminum chloride including dimethylaluminum chloride,diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminumchloride, and dihexylaluminum chloride; alkylaluminum dichlorideincluding methylaluminum dichloride, ethylaluminum dichloride,propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminumdichloride; and dialkylaluminum hydride including dimethylaluminumhydride, diethylaluminum hydride, dipropylaluminum hydride,diisobutylaluminum hydride and dihexylaluminum hydride. Among them,preferable is trialkylaluminum, and more preferable are triethylaluminumand triisobutylaluminum.

In the transition metal catalyst composition containing cocatalystaccording to the present invention, for preparing ethylene basedpolymers selected from ethylene homopolymers or copolymers of ethyleneand α-olefin, the transition metal compound and the cocatalyst havepreferably a molar ratio of transition metal (M):boron atom (B):aluminumatom (Al) in the range of 1:0˜100:1˜2,000, and more preferably1:0.5˜5:10˜500. The above ratio enables the preparation of the ethylenehomopolymers or the copolymers of ethylene and α-olefin, and the rangeof the ratio may be varied depending on purity of reaction.

According to another aspect of the present invention, the method ofpreparing ethylene based polymers by using the transition metal catalystcomposition may be carried out by contacting the transition metalcatalyst, cocatalyst, and ethylene or α-olefin comonomers, in thepresence of appropriate organic solvent. Here, the transition metalcatalyst and the cocatalyst components may be separately fed to thereactor, or those components may be mixed in advance and then fed to thereactor. The mixing conditions, such as the order of feeding,temperature, or concentration, are not particularly restricted.

Preferable examples of organic solvents usable in the preparing methodmay include (C3-C20) hydrocarbon, and specific examples thereof mayinclude butane, isobutane, pentane, hexane, heptane, octane, isooctane,nonane, decane, dodecane, cyclohexane, methylcyclohexane, benzene,toluene, xylene, and the like.

Specifically, ethylene may be used alone as the monomer, in thepreparation of the ethylene homopolymer. Here, the suitable pressure ofethylene may be 1˜1000 atm, and more preferably 6˜150 atm. Also,effectively, the polymerization reaction temperature may be 25° C.˜200°C., and preferably 50° C.˜180° C.

In addition, when the copolymer of ethylene and α-olefin is prepared, atleast one selected from straight or branched chain (C3-C18) α-olefin,(C5-C20) cycloolefin, styrene, and styrene derivatives, may be used ascomonomer, together with ethylene. Preferable examples of (C3-C18)α-olefin may be selected from the group consisting of propylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene,1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and1-octadecene; preferable examples of (C5-C20) cycloolefin may beselected from the group consisting of cyclopentene, cyclohexene,norbornene, and phenylnorbornene; and preferable examples of styrene andderivatives thereof may be selected from the group consisting ofstyrene, α-methylstyrene, p-methylstyrene, and 3-chloromethylstyrene. Inthe present invention, the above olefin may be copolymerized withethylene, or two or more kinds of olefin may be copolymerized withethylene. Here, preferable ethylene pressure and polymerization reactiontemperature are the same as the case where ethylene homopolymers areprepared. The copolymer prepared according to the method of the presentinvention may contain ethylene in a content of 30 wt % or more,preferably 60 wt % or more, and more preferably 60 to 99 wt %.

As described above, when the catalyst of the present invention is used,polymers from elastomers up to high density polyethylene (HDPE) thathave density of 0.850 g/cc to 0.960 g/cc and melt flow of 0.001 to 15dg/min can be easily and economically prepared by appropriately using(C4-C10) α-olefin as the comonomer and ethylene. Particularly, when thecatalyst of the present invention is used, copolymers having density of0.850 to 0.910 g/cc can be prepared at a high yield by using ethyleneand 1-butene.

In addition, ethylene/propylene (EP) elastomer can be excellentlyprepared by using the catalyst of the present invention.

In addition, when the ethylene homopolymer or copolymer according to thepresent invention is prepared, hydrogen may be used as a molecularweight regulator in order to regulate the molecular weight. The weightaverage molecular weight (Mw) thereof is generally in the range of 5,000to 1,000,000 g/mol.

Since the catalyst composition proposed by the present invention existsin a homogeneous state in the polymerization reactor, the catalystcomposition may be preferably employed in a solution polymerizationprocess carried out at a temperature higher than the melting point ofthe corresponding polymer. However, as disclosed by U.S. Pat. No.4,752,597, the transition metal compound and cocatalyst may be supportedon a porous metal oxide supporter, to thereby be used for slurrypolymerization or a gas phase polymerization process, as a heterogeneouscatalyst composition.

In addition, the present invention may include the compounds representedby Chemical Formulas 12 and 13 below, as an intermediate for preparingthe transition metal compound of Chemical Formula 1.

R₁ to R₉ and n each have the same definition as defined in ChemicalFormula 1, provided that there is excluded a case where all of R₁, R₂,R₃, R₆, R₇, R₈, and R₉ are hydrogen.

R₁ to R₉ and n each have the same definition as defined in ChemicalFormula 1.

The transition metal compound or the catalyst composition containing thetransition metal compound according to the present invention can beeasily prepared at a high synthesis yield in an economical manner.Further, the transition metal compound or the catalyst compositionaccording to the present invention can have excellent copolymerizationreactivity with other olefins while maintaining high catalytic activityeven at high temperature due to excellent thermal stability thereof andallow the preparation of high-molecular weight polymers at a high yield,resulting in higher commercial practicability as compared with thealready known metallocene and non-metallocene based single activationpoint catalysts. Therefore, the transition metal catalyst compositionaccording to the present invention can be usefully employed in thepreparation of ethylene based polymers selected from ethylenehomopolymers and copolymers of ethylene and α-olefin, having variousphysical properties.

Hereinafter, the embodiments of the present invention will be describedin detail with reference to accompanying Examples, which are notintended to restrict the scope of the invention.

Unless mentioned otherwise, all experiments for synthesizing ligands andcatalysts were carried out under nitrogen atmosphere by using standardSchlenk or glove-box techniques.

The organic solvents used in the reaction were subjected to reflux oversodium metal and benzophenone to thereby remove moisture, and thendistilled immediately before use. ¹H-NMR analyses of the synthesizedligands and catalysts were performed by using Bruker 500 MHz at roomtemperature.

Before use, n-heptane, as solvent for polymerization, was passed througha tube filled with molecular sieve 5 Å and activated alumina, andbubbled by high-purity nitrogen, to thereby sufficiently removemoisture, oxygen and other catalyst poison materials. The polymerizedpolymers were analyzed by the measurement methods described below.

1. Melt Flow Index (MI)

Measurement was conducted according to ASTM D 2839.

2. Density

Measurement was conducted by using density gradient tubes, according toASTM D 1505.

3. Melting Temperature (Tm)

Measurement was conducted in the conditions of 2^(nd) heating at a rateof 10° C./min under nitrogen atmosphere, by using Dupont DSC 2910.

4. Molecular Weight and Molecular Weight Distribution

Measurement was conducted at 135° C. at a rate of 1.0 mL/min in thepresence of 1,2,3-trichlorobenzene solvent, by using PL210 GPC equippedwith PL Mixed-BX2+preCol, and molecular weight was calibrated by usingPL polystyrene standards.

5. α-Olefin Content (Wt %) in Copolymer

Measurement was conducted by using 1,2,4-trichlorobenzene/C₆D₆ (7/3 byweight) mixture solvent at 120° C. in the ¹³C-NMR mode through BrukerDRX500 NMR spectrometer at 125 MHz. (Reference: Randal, J. C. JMS-Rev.Macromol. Chem. Phys. 1980, C29, 201)

The ratio of ethylene and α-olefin in EP polymers were quantified byusing an infrared spectrometer.

[Example 1] Preparation of Mixture of Complex 1 and Complex 2

Synthesis of 9,9-dihexyl-9H-fluorene

A 2000 mL round flask was charged with 9H-fluorene (50 g, 300.1 mmol)and potassium t-butoxide (77.0 g, 721.9 mmol), and then 700 mL of DMSOwas slowly injected thereto. 1-Bromohexane (119 g, 721.9 mmol) wasslowly added thereto from a dropping funnel under nitrogen atmosphere.The mixture was stirred at room temperature for 24 hours, and thereaction was terminated by addition of 500 mL of distilled water. Theorganic layer collected by extraction with n-hexane was dried overmagnesium sulfate, followed by removal of volatile materials, and thenpurified with n-hexane by using silica gel column chromatography,followed by drying and long-time storage at room temperature, to therebyobtain 90.0 g of 9,9-dihexyl-9H-fluorene (yield: 72.40%) as solid.

¹H-NMR (500 MHz, CDCl₃, ppm): δ=0.625-0.628 (m, 4H), 0.759-0.785 (m,6H), 1.050-1.125 (m, 12H), 1.953-1.983 (t, 4H), 7.293-7.340 (m, 6H),7.706-7.720 (d, 2H)

Synthesis of9,9-dihexyl-2-methyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one

A 2000 mL round flask was charged with 9,9-dihexyl-9H-fluorene (79 g,236.2 mmol) and 2-bromo-2-methylpropanoyl bromide (54.3 g, 236.2 mmol),and then dissolved with 600 mL of carbon disulfide inputted thereto.Then, the reactor was cooled with ice water. Under nitrogen atmosphere,aluminum trichloride (78.7 g, 590.4 mmol) was slowly added thereto inten lots over 2 hours. The mixture was stirred at room temperature for 8hours, and then the reaction was terminated by addition of 500 mL ofdistilled water, followed by washing 3 times with 500 mL of distilledwater. The organic layer was dried over magnesium sulfate, followed byremoval of volatile materials and drying, to thereby obtain 89.0 g of9,9-dihexyl-2-methyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one (yield:93.6%) as highly viscous oil.

¹H-NMR (500 MHz, CDCl₃, ppm): δ=0.601-0.627 (m, 4H), 0.741-0.774 (m,6H), 1.000-1.126 (m, 12H), 1.366-1.380 (d, 3H), 1.961-2.202 (m, 4H),2.789-2.801 (d, 2H), 3.445-3.498 (m, 1H), 7.375-7.383 (m, 3H), 7.731 (s,2H), 7.764-7.779 (d, 1H)

Synthesis of 9,9-dihexyl-2-methyl-1,2,3,9tetrahydrocyclopenta[b]fluoren-1-ol

In a 1000 mL round flask,9,9-dihexyl-2-methyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one (85 g,211.1 mmol) was dissolved in THF 400 mL and ethanol 400 mL, and thenstirred. Sodium borohydride (NaBH₄) (10 g, 265.0 mmol) was added to thereaction product in five lots, and then stirred for 12 hours. Theresultant mixture, after removal of solvent, was dissolved inethylacetate, and then washed with water three times. The organic layerwas dried over magnesium sulfate, followed by removal of volatilematerials and drying, to thereby obtain 82.0 g of9,9-dihexyl-2-methyl-1,2,3,9-tetrahydrocyclopenta[b]fluoren-1-ol (yield:96.0%) (two isomers), as highly viscous oil.

¹H-NMR (500 MHz, CDCl₃, ppm): δ=0.628-0.631 (m, 8H), 0.762-0.788 (m,12H), 1.109-1.136 (m, 24H), 1.198-1.212 (d, 3H), 1.314-1.327 (d, 3H),1.522-1.535 (d, 1H), 1.830-1.846 (d, 1H), 1.956-1.963 (m, 8H),2.323-2.352 (m, 1H), 2.525-2.572 (m, 1H), 2.628-2.655 (m, 1H),2.733-2.779 (m, 1H), 3.011-3.057 (m, 1H), 3.164-3.210 (m, 1H),4.783-4.812 (t, 1H), 5.052-5.077 (t, 1H), 7.289-7.380 (m, 8H), 7.525 (s,1H), 7.558 (s, 1H), 7.672-7.685 (d, 2H)

Synthesis of 9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluorene

In a 500 mL round flask,9,9-dihexyl-2-methyl-1,2,3,9-tetrahydrocyclopenta[b]fluoren-1-ol (80 g,197.7 mmol) and p-toluene sulfonic acid (0.2 g) were dissolved in 320 mLof toluene, and then water was completely removed under reflux withDean-Stark. The resultant material was cooled to room temperature, andthen an aqueous ammonium chloride solution (150 mL) and 200 mL ofdiethyl ether were injected thereto, followed by separation of theorganic layer. The organic layer collected by extracting the residuewith diethyl ether was dried over magnesium sulfate, followed by removalof volatile materials, and then purified by using silica gel columnchromatography tube, to thereby obtain 74.0 g of9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluorene (yield: 96.8%).

¹H-NMR (500 MHz, CDCl₃, ppm): δ=0.611-0.671 (m, 4H), 0.755-0.784 (m,6H), 1.041-1.140 (m, 12H), 1.943-1.976 (m, 4H), 2.200 (s, 3H), 3.373 (s,2H), 6.556 (s, 1H), 7.208-7.381 (m, 4H), 7.653-7.668 (d, 1H), 7.700 (s,1H)

Synthesis ofN-tert-butyl-1-(9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(9,9-dihexyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1l-dimethylsilanamine

In a 500 mL round flask,9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluorene (40.0 g, 103.5mmol) was dissolved in 320 mL of diethyl ether, and then the temperaturewas lowered to −78° C. Then, n-butyllithium (2.5M hexane solution, 42mL) was slowly injected thereto, followed by stirring at roomtemperature for 12 hours. After volatile materials were removed byvacuum, 350 mL of n-hexane was added to the mixture to lower the reactortemperature to −78° C., followed by addition of dichlorodimethylsilane(40 g). The temperature was again raised to room temperature, followedby stirring for 24 hours, and then salts were removed through filtering.Then, volatile materials were removed by vacuum. The product was againinputted to a 500 mL round flask, and dissolved in 320 mL of diethylether. The temperature was lowered to −78° C., and tert-butylamine (22.7g, 310.4 mmol) was added thereto. The temperature was raised to roomtemperature, followed by stirring for 12 hours, and then volatilematerials were completely removed by vacuum. Then, 200 mL of n-hexanewas added to dissolve the resultant material, and salts were removedthrough filtering. The solvent was removed, to thereby obtain 48 g of amixture ofN-tert-butyl-1-(9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(9,9-dihexyl-2-methyl-1,9-dihydrocylopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine(ratio=˜1:1), (yield: 88.9%), as viscous material.

1H-NMR (500 MHz, C₆D₆, ppm): δ=0.132 (s, 3H), 0.177-0.198 (d, 6H), 0.270(s, 1H), 0.804-0.879 (m, 12H), 0.973-1.295 (m, 50H), 2.170-2.348 (m,14H), 3.398-3.428 (d, 2H), 6.745 (s, 2H), 7.337-7.434 (m, 6H),7.518-7.908 (m, 6H)

Synthesis of(t-butylamido)dimethyl(9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanetitanium(IV)dimethyl(Complex 1) and(t-butylamido)dimethyl(9,9-dihexyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)silanetitanium(IV)dimethyl (Complex 2)

In a 500 mL round flask, the mixture ofN-tert-butyl-1-(9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(9,9-dihexyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine(ratio=˜1:1) (8.64 g, 16.75 mmol) was dissolved in 130 mL of diethylether, and then the temperature was lowered to −78° C. Then,methyllithium (1.5M diethyl ether solution, 49.4 mL) was slowly injectedthereto. The temperature was raised to room temperature, followed bystirring for 12 hours, to prepare lithium salt. In addition, in a drybox, TiCl₄ (16.75 mmol) and 150 mL of anhydrous n-hexane were inputtedto a 500 mL round flask, and then the temperature was lowered to −78° C.Then, the prepared lithium salt was slowly added thereto. Thetemperature was again raised to room temperature, followed by stirringfor 4 hours, and the solvent was removed by vacuum. The resultantmaterial was dissolved in n-hexane, and then the filtrate was extractedthrough filtering. Again, the solvent was removed by vacuum, to therebyobtain 8.1 g of a mixture of Complex 1 and Complex 2 (ratio ofapproximately 1:1), as solid.

1H-NMR (500 MHz, C₆D₆, ppm): δ=0.079-0.091 (d, 6H), 0.623-0.645 (d, 6H),0.813-1.336 (m, 56H), 1.601-1.619 (d, 18H), 2.071-2.514 (m, 14H),7.025-7.035 (d, 2H), 7.330-8.099 (m, 12H)

[Example 2] Preparation of Mixture of Complex 3 and Complex 4

Synthesis of 9,9-dimethyl-9H-fluorene

A 2000 mL round flask was charged with 9H-fluorene (50 g, 300.1 mmol)and potassium t-butoxide (77.0 g, 721.9 mmol), and then 700 mL of DMSOwas slowly injected thereto. Under nitrogen atmosphere, iodomethane(113.5 g, 800 mmol) was slowly dropped through a dropping funnel whilethe reactor temperature was maintained at 10° C. or lower. The mixturewas stirred at room temperature for 24 hours, and the reaction wasterminated by addition of 500 mL of distilled water. The organic layercollected by extraction with n-hexane was dried over magnesium sulfate,followed by removal of volatile materials, and then purified withn-hexane by using silica gel column chromatography tube, followed bydrying, to thereby obtain 47.5 g of 9,9-dimethyl-9H-fluorene (yield:81.50%) as white solid.

¹H-NMR (500 MHz, CDCl₃, ppm): δ=1.547 (s, 6H), 7.368-7.393 (t, 4H),7.488-7.499 (d, 2H), 7.777-7.791 (d, 2H)

Synthesis of 2,9,9-trimethyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one

A 2000 mL round flask was charged with 9,9-dimethyl-9H-fluorene (50 g,257.4 mmol) and 2-bromo-2-methylpropanoyl bromide (61.0 g, 265.1 mmol),and then dissolved with 700 mL of carbon disulfide inputted thereto.Then, the reactor was cooled with ice water. Under nitrogen atmosphere,aluminum trichloride (85.8 g, 643.4 mmol) was slowly added thereto inten lots over 2 hours. The mixture was stirred at room temperature for 8hours, and then the reaction was terminated by addition of 500 mL ofdistilled water. The resultant mixture was diluted by adding 500 mL ofmethyl chloride and washed with 500 mL of distilled water three times.The organic layer was dried over magnesium sulfate, followed by removalof volatile materials and drying, and then recrystallized by usingmethyl chloride and methanol, to thereby obtain 64.0 g of2,9,9-trimethyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one (yield: 94.8%)as white solid.

¹H-NMR (500 MHz, CDCl₃, ppm): δ=1.354-1.369 (d, 3H), 1.517 (s, 6H),2.784-2.811 (d, 2H), 3.444-3.496 (m, 1H), 7.376-7.429 (m, 2H),7.471-7.485 (d, 2H), 7.763 (s, 1H), 7.795-7.808 (d, 2H), 7.832 (s, 1H)

Synthesis of 2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluorene

In a 1000 mL round flask,2,9,9-trimethyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one (50 g, 190.6mmol) was dissolved THF 400 mL and ethanol 400 mL, and then stirred.Sodium borohydride (NaBH₄) (9.4 g, 247.8 mmol) was added to the reactionproduct in five lots, and then stirred for 12 hours. The resultantmixture, after removal of solvent, was dissolved in ethylacetate, andthen washed with water three times. The organic layer was dried overmagnesium sulfate, followed by removal of volatile materials. The driedreaction product was dissolved in 320 mL of toluene, and then inputtedto a 500 mL round flask. After that, p-toluene sulfonic acid (0.2 g) wasinputted thereto, and then water was completely removed under refluxwith Dean-Stark. The resultant material was cooled to room temperature,and then an aqueous ammonium chloride solution (150 mL) and 200 mL ofdiethyl ether were injected thereto, followed by separation of theorganic layer. The organic layer collected by extracting the residuewith diethyl ether was dried over magnesium sulfate, followed by removalof volatile materials, and then purified by using silica gel columnchromatography, to thereby obtain 42.0 g of2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluorene (yield: 89.42%).

¹H-NMR (500 MHz, CDCl₃, ppm): δ=1.515 (s, 6H), 2.203 (s, 3H), 3.375 (s,2H), 6.559 (s, 1H), 7.279-7.332 (m, 3H), 7.425-7.440 (d, 1H),7.697-7.711 (d, 1H), 7.740 (s, 1H)

Synthesis ofN-tert-butyl-1-(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(2,9,9-trimethyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine

In a 500 mL round flask,2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluorene (15.0 g, 60.9 mmol) wasdissolved in 300 mL of diethyl ether, and then the temperature waslowered to −78° C. Then, n-butyllithium (2.5M hexane solution, 24.8 mL)was slowly injected thereto, followed by stirring at room temperaturefor 12 hours. After the volatile materials were removed by vacuum, 350mL of n-hexane was added to the mixture to lower the reactor temperatureto −78° C., followed by addition of dichlorodimethylsilane (23 g). Thetemperature was again raised to room temperature, followed by stirringfor 24 hours, and then salts were removed through filtering. Then,volatile materials were removed by vacuum. The product was againinputted to a 500 mL round flask, and dissolved in 320 mL of diethylether. The temperature was lowered to −78° C., and tert-butylamine (16.1g, 152.2 mmol) was added thereto. The temperature was raised to roomtemperature, followed by stirring for 12 hours, and then volatilematerials were completely removed by vacuum. Then, 200 mL of toluene wasadded to dissolve the resultant material, and salts were removed throughfiltering. The solvent was removed, to thereby obtain 21.0 g of amixture ofN-tert-butyl-1-(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(2,9,9-trimethyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine(yield: 91.8%), as a viscous material.

¹H-NMR (500 MHz, C₆D₆, ppm): δ=0.085-0.098 (d, 6H), 0.229-0.253 (d, 6H),0.555 (s, 2H), 1.161-1.179 (d, 18H), 1.534-1.559 (d, 12H), 2.304 (s,6H), 3.385-3.422 (d, 2H), 6.747 (s, 2H), 7.303-8.049 (m, 12H)

Synthesis of(t-butylamido)dimethyl(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanetitanium(IV)dimethyl (Complex 3) and(t-butylamido)dimethyl(2,9,9-trimethyl-1,9-dihydrocyclochloropenta[b]fluoren-1-yl)silanetitanium(IV)dimethyl (Complex 4)

In a 250 mL round flask, the mixture ofN-tert-butyl-1-(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(2,9,9-trimethyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine(10.4 g, 27.69 mmol) was dissolved in 200 mL of diethyl ether, and thenthe temperature was lowered to −78° C. Then, methyllithium (1.5M diethylether solution, 75.6 mL) was slowly injected thereto. The temperaturewas raised to room temperature, followed by stirring for 12 hours, toprepare lithium salt. In addition, in a dry box, TiCl₄ (5.25 g, 27.69mmol) and 150 mL of anhydrous n-hexane were inputted to a 500 mL roundflask, and then the temperature was lowered to −78° C. Then, theprepared lithium salt was slowly added thereto. Again, the temperaturewas raised to room temperature, followed by stirring for 4 hours, andthen the solvent was removed by vacuum. The resultant material was againdissolved in toluene, and then the undissolved part was removed throughfiltering. Again, toluene was removed by vacuum, to thereby obtain 10.8g of a mixture of Complex 3 and Complex 4, as solid.

¹H-NMR (500 MHz, C₆D₆, ppm): δ=−0.019-−0.010 (d, 6H), 0.641-0.647 (d,6H), 0.794-2.212 (m, 48H), 7.004-7.025 (d, 2H), 7.106-8.092 (m, 12H)

[Example 3] Preparation of Mixture of Complex 5 and Complex 6

Synthesis ofN-cyclohexal-1-(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-cyclohexyl-1-(2,9,9-trimethyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine

In a round flask, 2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluorene (7.5g, 30.5 mmol) was dissolved in 300 mL of diethyl ether, and then thetemperature was lowered to −78° C. Then, n-butyllithium (2.5M hexanesolution, 12.4 mL) was slowly injected thereto, followed by stirring atroom temperature for 12 hours. After the volatile materials were removedby vacuum, 200 mL of n-hexane was added to the mixture to lower thereactor temperature to −78° C., followed by addition ofdichlorodimethylsilane (11.8 g, 91.4 mmol). The temperature was againraised to room temperature, followed by stirring for 24 hours, and thensalts were removed through filtering. Then, volatile materials wereremoved by vacuum. The product was again inputted to a 200 mL roundflask, and dissolved in 150 mL of diethyl ether. The temperature waslowered to −78° C., and cyclohexaneamine (9.05 g, 91.4 mmol) was addedthereto. The temperature was raised to room temperature, followed bystirring for 12 hours, and then volatile materials were completelyremoved by vacuum. Then, 100 mL of toluene was added to dissolve theresultant material, and salts were removed through filtering. Thesolvent was removed, to thereby obtain 10.6 g of a mixture ofN-cyclohexyl-1-(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-cyclohexyl-1-(2,9,9-trimethyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine,as viscous material.

Synthesis of(cyclohexylamido)dimethyl(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanetitanium(IV)dimethyl (Complex 5) and(cyclohexylamido)dimethyl(2,9,9-trimethyl-1,9-dihydrocyclochloropenta[b]fluoren-1-yl)silanetitanium(IV)dimethyl (Complex 6)

In a 250 mL of three-neck round flask, the well-dried mixture ofN-cyclohexyl-1-(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-cyclohexyl-1-(2,9,9-trimethyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine(10.6 g, 26.39 mmol) was dissolved in 200 mL of diethyl ether, and thenthe temperature was lowered to −78° C. Then, methyllithium (1.5M diethylether solution, 72.1 mL) was slowly injected thereto. The temperaturewas raised to room temperature, followed by stirring for 12 hours, toprepare lithium salt. In addition, in a dry box, TiCl₄ (5.00 g, 26.39mmol) and 150 mL of anhydrous n-hexane were inputted to a 500 mL roundflask, and then the temperature was lowered to −78° C. Then, theprepared lithium salt was slowly added thereto. Again, the temperaturewas raised to room temperature, followed by stirring for 4 hours, andthen the solvent was removed by vacuum. The resultant material was againdissolved in toluene, and then the undissolved part was removed throughfiltering. Again, toluene was removed by vacuum, to thereby obtain 11.5g of a mixture of Complex 5 and Complex 6, as solid.

¹H-NMR (500 MHz, C₆D₆, ppm): δ=−0.070-−0.049 (d, 6H), 0.628-0.634 (d,6H), 0.764-2.195 (m, 50H), 4.779 (m, 2H), 6.985-7.002 (d, 2H),7.100-8.095 (m, 12H)

[Example 4] Preparation of Mixture of Complex 7 and Complex 8

Synthesis of 9,9-ditetradecyl-9H-fluorene

A 2000 mL round flask was charged with 9H-fluorene (15 g, 90.24 mmol)and potassium tert-butoxide (21.2 g, 198.5 mmol), and then 300 mL ofDMSO was slowly injected thereto. Under nitrogen atmosphere,1-bromotetradecane (54 g, 198.5 mmol) was slowly dropped through adropping funnel while the reactor temperature was maintained at 10° C.or lower. The mixture was stirred at room temperature for 24 hours, andthe reaction was terminated by addition of 500 mL of distilled water.The organic layer collected by extraction with n-hexane was dried overmagnesium sulfate, followed by removal of volatile materials, and thenpurified with n-hexane by using silica gel column chromatography tube,followed by drying, to thereby obtain 42.0 g of9,9-ditetradecyl-9H-fluorene (yield: 83.26%) as white solid.

¹H-NMR (500 MHz, CDCl₃, ppm): δ=0.616-0.634 (m, 4H), 0.881-0.909 (m,6H), 1.051-1.323 (m, 44H), 1.951-1.984 (t, 4H), 7.292-7.355 (m, 6H),7.708-7.722 (d, 2H)

Synthesis of2-methyl-9,9-ditetradecyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one

A 5000 mL round flask was charged with9,9-ditetradecylmethyl-9H-fluorene (30 g, 53.7 mmol) and2-bromo-2-methylpropanoyl bromide (12.7 g, 55.3 mmol), and thendissolved with 300 mL of carbon disulfide inputted thereto. Then, thereactor was cooled with ice water. Under nitrogen atmosphere, aluminumtrichloride (15.7 g, 118.1 mmol) was slowly added thereto in ten lotsover 2 hours. The mixture was stirred at room temperature for 8 hours,and then the reaction was terminated by addition of 100 mL of distilledwater, followed by washing with 500 mL of distilled water three times.The organic layer was dried over magnesium sulfate, followed by removalof volatile materials and drying, to thereby obtain 30.0 g of2-methyl-9,9-ditetradecyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one(yield: 89.1%) as highly viscous oil.

¹H-NMR (500 MHz, CDCl₃, ppm): δ=0.590 (m, 4H), 0.867-0.895 (m, 6H),1.024-1.295 (m, 44H), 1.367-1.382 (d, 3H), 1.963-2.204 (t, 4H),2.792-2.826 (d, 2H), 3.448-3.500 (m, 1H), 7.372-7.400 (m, 3H),7.726-7.780 (m, 3H)

Synthesis of 2-methyl-9,9-ditetradecyl-3,9-dihydrocyclopenta[b]fluorene

In a 500 mL round flask,2-methyl-9,9-ditetradecyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one (20g, 31.9 mmol) was dissolved in 150 mL of THF and 150 mL of ethanol, andthen stirred. Sodium borohydride (NaBH₄) (1.8 g, 47.8 mmol) was added tothe reactant in five lots, and then stirred for 12 hours. The resultantmixture, after removal of solvent, was dissolved in ethylacetate, andthen washed with water three times. The organic layer was dried overmagnesium sulfate, followed by removal of volatile materials. The driedreactant was dissolved in 150 mL of toluene, and then inputted to around flask. After that, p-toluene sulfonic acid (0.08 g) was inputtedthereto, and then water was completely removed under reflux withDean-Stark. The resultant material was cooled to room temperature, andthen an aqueous ammonium chloride solution (100 mL) and 200 mL ofdiethyl ether were injected thereto, followed by separation of theorganic layer. The organic layer collected by extracting the residuewith diethyl ether was dried over magnesium sulfate, followed by removalof volatile materials, and then purified by using silica gel columnchromatography, to thereby obtain 15.3 g of2-methyl-9,9-ditetradecyl-3,9-dihydrocyclopenta[b]fluorene (yield:78.5%).

¹H-NMR (500 MHz, CDCl₃, ppm): δ=0.649-0.665 (m, 4H), 0.891-0.918 (m,6H), 1.059-1.319 (m, 44H), 1.953-1.986 (t, 4H), 2.206 (s, 3H), 3.378 (s,2H), 6.562 (s, 1H), 7.237-7.332 (m, 4H), 7.663-7.678 (d, 1H), 7.710 (s,1H)

Synthesis ofN-tert-butyl-1-(9,9-ditetradecyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(9,9-ditetradecyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine

In a 250 mL round flask,2-methyl-9,9-ditetradecyl-3,9-dihydrocyclopenta[b]fluorene (4.9 g, 8.0mmol) was dissolved in 100 mL of anhydrous diethyl ether, and then thetemperature was lowered to −78° C. Then, n-butyllithium (1.6M hexanesolution, 5.5 mL) was slowly injected thereto, followed by stirring atroom temperature for 12 hours. After volatile materials were removed byvacuum, 100 mL of n-hexane was added to the mixture to lower the reactortemperature to −78° C., followed by addition of dichlorodimethylsilane(2.9 g). The temperature was again raised to room temperature, followedby stirring for 24 hours, and then salts were removed through filtering.Then, volatile materials were removed by vacuum. The product was againinputted to a 250 mL round flask, and dissolved in 100 mL of diethylether. The temperature was lowered to −78° C., and tert-butylamine (1.8g, 24.1 mmol) was added thereto. The temperature was raised to roomtemperature, followed by stirring for 12 hours, and then volatilematerials were completely removed by vacuum. Then, 200 mL of n-hexanewas added to dissolve the resultant material, and salts were removedthrough filtering. The solvent was removed, to thereby obtain 5.5 g of amixture ofN-tert-butyl-1-(9,9-ditetradecyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(9,9-ditetradecyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine(ratio=˜1:1), (yield: 92.7%), as high viscous material.

¹H-NMR (500 MHz, C₆D₆, ppm): δ=0.145 (s, 3H), 0.183-0.204 (d, 6H), 0.290(s, 3H), 0.552 (s, 1H), 0.603 (s, 1H), 0.998-1.370 (m, 126H),2.228-2.301 (m, 14H), 3.408-3.435 (d, 2H), 6.749-6.760 (d, 2H),7.353-7.461 (m, 6H), 7.546-8.073 (m, 6H)

Synthesis of(t-butylamido)dimethyl(9,9-ditetradecyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanetitanium(IV)dimethyl(Complex 7) and(t-butylamido)dimethyl(9,9-ditetradecyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)silanetitanium(IV)dimethyl (Complex 8)

In a 250 mL round flask, a mixture ofN-tert-butyl-1-(9,9-ditetradecyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamineandN-tert-butyl-1-(9,9-ditetradecyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine(ratio=˜1:1) (5.0 g, 6.8 mmol) was dissolved in 100 mL of diethyl ether,and then the temperature was lowered to −78° C. Then, methyllithium(1.5M diethyl ether solution, 18.5 mL) was slowly injected thereto. Thetemperature was raised to room temperature, followed by stirring for 12hours, to prepare lithium salt. In addition, in a dry box, TiCl₄ (16.75mmol) and 50 mL of anhydrous n-hexane were inputted to a 250 mL roundflask, and then the temperature was lowered to −78° C. Then, theprepared lithium salt was slowly added thereto. The temperature wasagain raised to room temperature, followed by stirring for 4 hours, andthe solvent was removed by vacuum. The resultant material was dissolvedin n-hexane, and then the filtrate was extracted through filtering.Again, n-hexane was removed by vacuum, to thereby obtain 5.2 g of amixture of Complex 7 and Complex 8 (ratio of approximately 1:1), assolid.

¹H-NMR (500 MHz, C₆D₆, ppm): δ=0.093-0.104 (d, 6H), 0.630-0.647 (d, 6H),0.856-1.392 (m, 120H), 1.609-1.643 (d, 18H), 2.095-2.214 (m, 14H),7.023-7.041 (d, 2H), 7.305-8.097 (m, 12H)

[Example 5] Preparation of Complex 9

Synthesis of 1,2,9,9-tetramethyl-3,9-dihydrocyclopenta[b]fluorene

In a 1000 mL round flask,2,9,9-trimethyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one (50 g, 190.6mmol) was dissolved in 400 mL of toluene, and then the temperature waslowered to 0° C. Then, 76 mL of 3M methylmagnesium bromide (THFsolution) was slowly injected thereto, followed by stirring at roomtemperature for 12 hours. The reaction product was poured into a mixtureof 200 mL of 1N-HCl aqueous solution and 200 g of ice. The mixture wasstirred for 1 hour, followed by extraction with toluene, and then theorganic layer was dried over magnesium sulfate, followed by removal ofvolatile materials. The dried reaction product was dissolved in 320 mLof toluene, and then inputted to a 500 mL round flask. After that,p-toluene sulfonic acid (0.2 g) was inputted thereto, and then water wascompletely removed under reflux with Dean-Stark. The resultant materialwas cooled to room temperature, and then an aqueous ammonium chloridesolution (150 mL) and 200 mL of diethyl ether were injected thereto,followed by separation of the organic layer. The organic layer collectedby extracting the residue with diethyl ether was dried over magnesiumsulfate, followed by removal of volatile materials, and then purified byusing silica gel column chromatography, to thereby obtain 42.0 g of1,2,9,9-tetramethyl-3,9-dihydrocyclopenta[b]fluorene (yield: 84.6%).

¹H-NMR (500 MHz, CDCl₃, ppm): δ=1.547-1.568 (d, 6H), 2.123 (s, 6H),3.352 (s, 2H), 7.273-7.363 (m, 3H), 7.442-7.456 (d, 1H), 7.711-7.45723(m, 2H)

Synthesis ofN-tert-butyl-1,1-dimethyl-1-(1,2,9,9-tetramethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanamine

In a 500 mL round flask,1,2,9,9-tetramethyl-3,9-dihydrocyclopenta[b]fluorene (15.0 g, 57.6 mmol)was dissolved in 300 mL of diethyl ether, and then the temperature waslowered to −78° C. Then, n-butyllithium (2.5M hexane solution, 25.4 mL)was slowly injected thereto, followed by stirring at room temperaturefor 12 hours. After the volatile materials were removed by vacuum, 350mL of n-hexane was added to the mixture, to lower the reactortemperature to −78° C., followed by addition of dichlorodimethylsilane(23 g). The temperature was again raised to room temperature, followedby stirring for 24 hours, and then salts were removed through filtering.Then, volatile materials were removed by vacuum. The product was againinputted to a 500 mL round flask, and dissolved in 320 mL of diethylether. The temperature was lowered to −78° C., and tert-butylamine (10.5g, 144.0 mmol) was added thereto. The temperature was raised to roomtemperature, followed by stirring for 12 hours, and then volatilematerials were completely removed by vacuum. Then, 200 mL of toluene wasadded to dissolve the resultant material, and salts were removed throughfiltering. The solvent was removed, to thereby obtain 20.0 g ofN-tert-butyl-1,1-dimethyl-1-(1,2,9,9-tetramethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanamine(yield: 89.1%), as viscous material.

¹H-NMR (500 MHz, C₆D₆, ppm): δ=0.166 (s, 3H), 0.222 (s, 3H), 0.610 (s,1H) 1.239 (s, 9H), 1.618-1.651 (d, 6H), 2.256 (s, 6H), 3.437 (s, 1H),7.361-7.466 (m, 3H), 7.590 (s, 1H), 7.958-7.973 (d, 1H), 8.128 (s, 1H)

Synthesis of(t-butylamido)-1,1-dimethyl(1,2,9,9-tetramethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanetitanium(IV)dimethyl (Complex 9)

In a 250 mL round flask,N-tert-buty-1,1-dimethyl-1-(1,2,9,9-tetramethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-silanamine(10.8 g, 27.7 mmol) was dissolved in 200 mL of diethyl ether, and thenthe temperature was lowered to −78° C. Then, methyllithium (1.5M diethylether solution, 75.76 mL) was slowly injected thereto. The temperaturewas raised to room temperature, followed by stirring for 12 hours, toprepare lithium salt. In addition, in a dry box, TiCl₄ (5.26 g, 27.7mmol) and 150 mL of anhydrous n-hexane were inputted to a 500 mL roundflask, and then the temperature was lowered to −78° C. Then, theprepared lithium salt was slowly added thereto. Again, the temperaturewas raised to room temperature, followed by stirring for 4 hours, andthen the solvent was removed by vacuum. The resultant material was againdissolved in toluene, and then the undissolved part was removed throughfiltering. Again, toluene was removed by vacuum, to thereby obtain 10.8g of Complex 9 as solid.

¹H-NMR (500 MHz, C₆D₆, ppm): δ=−0.018 (s, 3H), 0.677 (s, 3H), 0.819 (s,3H), 0.875 (s, 3H), 1.562-1.584 (m, 15H), 2.104 (s, 3H), 2.423 (s, 3H),7.091-7.407 (m, 3H), 7.680-7.712 (m, 2H), 8.141 (s, 1H)

[Comparative Preparation Example 1] Preparation of(t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(IV)dimethyl

The(t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(IV)dimethyl compound was prepared by dissolving(t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(IV)dichloride purchased from Boulder Scientific Company of U.S., in diethylether, lowering the temperature to −78° C., and then reacting it with 2equivalents of metal lithium.

Copolymerization of Ethylene and 1-Octene [Examples 6 to 12 andComparative Examples 1 and 2] Copolymerization of Ethylene and 1-Octeneby Continuous Solution Polymerization Process

Copolymerization of ethylene and 1-octene was carried out by using acontinuous type polymerization apparatus as follows.

The catalysts synthesized in Examples 1 to 5 and Comparative PreparationExample 1 were used as single activation point catalysts, andcyclohexane was used as the solvent. The amounts of catalysts used aredescribed in Table 1 below. Ti, Al, and B indicate a single activationpoint catalyst, triisobutyl aluminum as a cocatalyst, andtriphenylmethyl tetrakis(pentafluorophenyl)borate, respectively. Therespective catalysts were injected while they each were dissolved intoluene in a concentration of 0.2 g/l, and the synthesis was carried outby using 1-octene as comonomer. The conversion ratio of the reactor maybe estimated through reaction conditions and temperature gradient in thereactor when one kind of polymer was prepared by polymerization in therespective reaction conditions. The molecular weight, in the case of asingle activation point catalyst, was controlled as a function of thereactor temperature and the content of 1-octene, and conditions andresults of the polymerization are shown in Table 1 below.

TABLE 1 Example 6 Example 7 Example 8 Example 9 Example 10Polymerization Catalyst Example 1 Example 1 Example 1 Example 2 Example3 conditions Total solution flux (kg/h) 5 5 5 5 5 Feeding amount ofethylene (w %) 8 6 6 6 6 Feeding molar ratio of 0.3 0.3 0.3 0.2 0.181-octene to ethylene (1-C8/C2) Feeding amount of Ti (μmol/kg) 4 3 3 2.54 Al/Ti ratio 45 50 50 60 45 B/Ti ratio 3 3 3 3 3 Reaction Temperature(° C.) 120 110 110 100 100 Polymerization C2 conversion ratio (%) 96 9794 97 92 results MI 0.7 0.85 0.14 1.1 1.2 Density (g/cc) 0.865 0.8620.871 0.851 0.852 Weight average molecular weight 98,300 95,400 127,40091,400 90,200 Molecular weight distribution index 1.9 2.0 2.2 2.1 2.0Comparative Comparative Example 11 Example 12 Example 1 Example 2Polymerization Catalyst Example 4 Example 5 Comparative Comparativeconditions Preparation Preparation Example 1 Example 1 Total solutionflux (kg/h) 5 5 5 5 Feeding amount of ethylene (w %) 6 6 8 8 Feedingmolar ratio of 0.3 0.2 0.22 0.19 1-octene to ethylene (1-C8/C2) Feedingamount of Ti (μmol/kg) 3 2.2 2 1.5 Al/Ti ratio 50 70 75 100 B/Ti ratio 33 3 3 Reaction Temperature (° C.) 120 100 113 104 Polymerization C2conversion ratio (%) 98 98 94 92 results MI 0.9 0.39 12.3 5.0 Density(g/cc) 0.865 0.869 0.875 0.878 Weight average molecular weight 94,500108,000 62,400 72,000 Molecular weight distribution index 2.0 2.1 1.71.8 Ti: Ti in the single activation point catalyst Al:Triisobutylaluminum as cocatalyst B: Triphenylmethyltetrakis(pentafluorenyl)borate as cocatalyst

It can be seen from Examples 6 to 12 and Comparative Examples 1 and 2,in Examples 6 to 12 polymerized by using the catalyst developed in thepresent invention as compared with Comparative Examples 1 and 2,polymers having a high conversion ratio of ethylene even under theconditions of high-temperature (100° C. or higher), low density, and alow MI value meaning high molecular weight, can be easily obtained.

Copolymerization of Ethylene and 1-Butene [Examples 13 to 15]Copolymerization of Ethylene and 1-Butene by Continuous SolutionPolymerization Process

Copolymerization of ethylene and 1-butene was carried out by using acontinuous type polymerization apparatus, in the same method as thecopolymerization of ethylene and 1-octene by the continuous solutionpolymerization mentioned in Examples 6 to 12 except that 1-butene wasused as the comonomer, as follows. Detailed polymerization conditionsand polymerization results are shown in Table 2 below.

TABLE 2 Example Example Example 13 14 15 Polymerization Catalyst Example1 Example 1 Example 1 conditions Total solution 5 5 5 flux (kg/h)Feeding amount 6 6 6 of ethylene (w %) Feeding molar 0.6 0.5 0.4 ratioof 1-butene to ethylene (1-C4/C2) Feeding amount 4 3.5 3 of Ti (μmol/kg)Al/Ti ratio 45 48 50 B/Ti ratio 3 3 3 Reaction 104 101 101 Temperature(° C.) Polymerization C2 conversion 99 98 96 results ratio (%) MI 0.70.36 0.19 Density (g/cc) 0.860 0.863 0.865 Weight average 98,200 109,400121,200 molecular weight Molecular weight 1.9 2.2 2.3 distribution indexTi: Ti in the single activation point catalyst Al: Triisobutylaluminumas cocatalyst B: Triphenylmethyl tetrakis(pentafluorenyl)borate ascocatalyst

It can be seen from Table 2 above, that, in Examples 13 to 15polymerized by using the catalyst developed in the present invention,ultralow density elastomers having a high conversion ratio of ethyleneeven under the conditions of high temperature (100° C. or higher) andhigh molecular weight even with using a small amount of 1-butene(1-C4/C2 molar ratio=0.4) can be easily obtained at a high yield.

The present invention has been described in detail with reference toexamples as set forth above, but those skilled in the art to which theinvention pertains can make various modifications without departing fromthe spirit and scope of the invention defined in appended claims.Therefore, alterations and modifications of the examples of the presentinvention would not depart from the technique of the present invention.

The invention claimed is:
 1. A compound of chemical formula 13:

In Chemical Formula 13, R₁ is hydrogen, (C1-C50)alkyl,halo(C1-C50)alkyl, (C3-C50)cycloalkyl, (C6-C30)aryl,(C6-C30)aryl(C1-C50)alkyl, ((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl,—NR^(a)R^(b), SiR^(c)R^(d)R^(e), or 5- through 7-memberedN-heterocycloalkyl containing at least one nitrogen atom; R₂ and R₃ eachare independently hydrogen, (C1-C50)alkyl, (C1-C50)alkoxy,halo(C1-C50)alkyl, (C3-C50)cycloalkyl, (C6-C30)aryl, (C6-C30)aryloxy,(C1-C50)alkyl(C6-C30)aryloxy, (C6-C30)aryl(C1-C50)alkyl,((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl, —NR^(a)R^(b) or—SiR^(c)R^(d)R^(e); R₄ and R₅ each are independently (C1-C50)alkyl,halo(C1-C50)alkyl, (C3-C50)cycloalkyl, (C6-C30)aryl,(C6-C30)aryl(C1-C50)alkyl, ((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl,—NR^(a)R^(b), or —SiR^(c)R^(d)R^(e); R₆, R₇, R₈ and R₉ each areindependently hydrogen, (C1-C50)alkyl, halo(C1-C50)alkyl,(C3-C50)cycloalkyl, (C1-C50)alkoxy, (C6-C30)aryl,(C6-C30)aryl(C1-C50)alkyl, ((C1-C50)alkyl(C6-C30)aryl)(C1-C50)alkyl,(C6-C30)aryloxy, (C1-C50)alkyl(C6-C30)aryloxy, N-carbazolyl,—NR^(a)R^(b), or —SiR^(c)R^(d)R^(e), or may be linked to an adjacentsubstituent via (C1-C5)alkylene to form a ring, and at least one —CH₂—of the alkylene may be substituted by a hetero atom selected from —O—,—S—, and —NR′—, and the alkylene may be further substituted with(C1-C50)alkyl; aryl of R₁ to R₉ may be further substituted with at leastone substituent selected from the group consisting of (C1-C50)alkyl,halo(C1-C50)alkyl, (C1-C50)alkoxy, (C6-C30)aryloxy, (C6-C30)aryl,(C1-C50)alkyl(C6-C30)aryl, and (C6-C30)aryl(C1-C50)alkyl; R′ and R^(a)to R^(e) each are independently (C1-C50)alkyl or (C6-C30)aryl; n is aninteger of 1 or 2, each R₁ may be the same or different when n is 2.